Process for preparing single crystal

ABSTRACT

A process for preparing a single crystal comprising drawing up a single crystal by the Czochralski process and cooling it at a temperature not lower than 600° C. at a reduced pressure or in vacuo, by which a single crystal having a dislocation density of 1.5×10 4  cm 2  or less is prepared.

FIELD OF THE INVENTION

The present invention relates to a process for preparing a single crystal. More particularly, it relates to an improved Czochralski process for preparing a single crystal by pulling up it from a melt raw material.

BACKGROUND OF THE INVENTION

A single crystal is a piece of material which forms one crystal and has a substantially homogeneous atomic sequence throughout the whole piece.

Processes for preparing the single crystal can be roughly classified into two groups, namely a solution process and a melt process. The single crystal of a salt is usually prepared by the solution process. However, the solution process is greatly influenced by impurities and/or different kinds of ions while the melt process less suffers such the drawbacks.

As the melt process, there are known several processes including the Kyropoulos process, the Stober-Stockbarger process, the Verneuli process and the Czochralski process.

The Czochralski process is now briefly explained by making reference to FIG. 1. A surface of a melted raw material 1 is covered with melted B₂ O₃ 2. A seed crystal 3 contacts the surface of the melted material 1 and pulls up a single crystal 4 with rotation. In FIG. 1, numerals 5 and 6 denote a crucible and a heater respectively.

In order to maintain a stoichiometric composition of a semiconducting compound containing a volatile component, namely an atom having a high vapor pressure (eg. GaP, GaAs, InP, etc.), the whole system is contained in a high-pressure chamber 7 as shown in FIG. 1, which is pressurized to a pressure higher than 2 Kg/cm² with inert gas 8 (eg. argon, nitrogen, etc.). After grown at the high pressure, the single crystal 4 is cooled to a room temperature at the same high pressure and then removed from the chamber 7.

During the cooling at the high pressure, convection flow of the high-pressure gas is so vigorous that the single crystal is quickly cooled, which may results in strain in the crystal and a large dislocation density. For example, the dislocation density in the conventional single crystal is as high as 2-5×10⁴ cm⁻².

SUMMARY OF THE INVENTION

One object of the invention is to provide a single crystal having a low dislocation density.

Another object of the invention is to provide a process for preparing a single crystal which prevents development of strain in the single crystal and affords a single crystal having a low dislocation density.

These and other objects of the invention can be accomplished by a process of the invention which comprises pulling up a single crystal by the Czochralski process and cooling it at a temperature not lower than 600° C. at a reduced pressure or in vacuo.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of an apparatus to be used to carry out the Czochralski process, and

FIG. 2 shows average dislocation densities of the single crystals prepared by the process of the invention and the conventional process.

DETAILED DESCRIPTION OF THE INVENTION

The process of the invention is suitable to prepare a single crystal of a semiconducting compound containing a volatile component which has been prepared by the Czochralski process. Specific examples of such compound are those consisting of atoms of the groups III-V in the periodic table such as GaP, GaAs and InP, and those consisting of atoms of the groups II-VI in the periodic table such as ZnSe and CdS.

Now referring to the figures, FIG. 1 shows the single crystal 4 after drawn up. The single crystal 4 is pulled up at a high temperature higher than 800° C. (for example, about 1,240° C. in case of GaAs) and a high pressure of 2 to 60 Kg/cm² and then gradually (at a rate of 0.2 to 4 cm/hr.) pulled up through the layer of melted B₂ O₃ 2 to the height of about 1 to 10 cm from the surface of the melted B₂ O₃ 2.

Thereafter, the single crystal is cooled at a rate of 1° to 2° C./min. to a temperature from 800° to 1100° C. (for example about 1,000° C. in case of GaAs) and kept at the same temperature for 1 to 2 hours. The pressure of the inert gas 8 is gradually (at a rate of up to 60 Kg/cm² /hr.) decreased to 1 to 3 Kg/cm² at the same temperature and kept under the same conditions for 1 to 2 hours.

Then, the single crystal is cooled to a temperature not lower than 600° C. (for example, about 800° C. in case of GaAs) at a rate of 1° to 2° C./min. At the same temperature, the interior of the chamber 7 is gradually (at a rate of up to 10 Torr/hr.) evacuated (for example, 10⁻² Torr or lower in case of GaAs), and such vacuum is kept at the same temperature for 1 to 2 hours. After cooling the chamber to a room temperature at a rate of 15° C./min., the single crystal 4 is removed from the chamber.

In the process of the invention, the procedures lowering the pressure and the temperature are not limited to those described above. The essential feature of the invention is cooling the single crystal at a temperature not lower than 600° C. at reduced pressure, for example 1 to 3 Kg/cm² or in vacuo. Practically, pressure is preferably lowered by two steps as described above since it is difficult to evacuated the chamber at a relatively high temperature. When the crystal is subjected to a low pressure at a temperature lower than 600° C., it is easily cooled and tends to be strained and thus the dislocation density tends to be large.

Since little or no convection of the gas occurs when the single crystal is cooled at the low pressure or in vacuo according to the process of the invention, the single crystal is gradually cooled by radiation and, therefore, it is less strained and has a lower dislocation density, for example 1.5×10⁴ cm⁻² of less, preferably 0.5-1×10⁴ cm⁻².

The present invention will be hereinafter explained further in detail by following Examples.

EXAMPLES

In the apparatus shown in FIG. 1, a single crystal of semiconducting GaAs was grown by pulling it up at 1238° C. and 15 Kg/cm² in <100> direction to obtain the single crystal having a diameter of 50 mm and a length of 100 mm.

The thus formed single crystal was gradually (at a rate of 3° C./min.) cooled to about 1,000° C. at 15 Kg/cm² and then, at the same temperature, the pressure was reduced to 3 Kg/cm² at a rate of 6 Kg/cm² /hr. and kept at the same pressure for one hour.

Then, the single crystal was cooled to about 800° C. at a rate of 1° to 2° C./min. and at the same temperature, the pressure was gradually (at a rate of 0.1 Kg/cm² /min.) reduced to atmospheric pressure and further gradually (at a rate of 10 Torr/min.) evacuated to 10⁻² Torr. After kept at the same temperature and pressure for two hours, the single crystal was cooled to a room temperature at a rate of 2° to 3° C./min.

As a comparative example, the formed single crystal was cooled to 800° C. at 15 Kg/cm² and kept at the same temperature for two hours. Thereafter, the single crystal was cooled to a room temperature, at which the pressure was about 7.5 Kg/cm².

A wafer of (100) lattice plane was prepared from the front lower part of the each single crystal and etched with a KOH etchant. The obtained etching pitch was observed. The results are shown in FIG. 2. As apparent from FIG. 2, the average dislocation density of the single crystal obtained by the conventional process is 2 to 5×10⁴ cm⁻² while the average dislocation density of the one obtained by the process of the invention is 0.5 to 1×10⁴ cm⁻² and the scatter is less. 

What is claimed is:
 1. A process for preparing a single crystal comprising pulling up a single crystal by the Czochralski process and cooling it at a temperature not lower than 600° C. at a reduced pressure or in vacuo wherein the cooling step of the pulled single crystal comprises lowering the temperature at a rate of up to 5° C./min. to a temperature higher than 600° C., keeping the same temperature for 1 to 2 hours, reducing the pressure at the same temperature at a rate of up to 60 Kg/cm² /hr. to 1 to 3 kg/cm², keeping the same pressure for 1 to 2 hours, lowering the temperature at the same pressure for 1 to 2 hours, lowering the temperature at the same pressure at a rate of up 5° C./min. to a temperature not lower than 600° C., reducing the pressure at the same temperature at a rate of up to 60 Kg/cm² /hr. to atmospheric pressure, evacuating at a rate of up to 10 Torr/min. to a pressure of 10⁻² Torr. or lower, and keeping the same vacuum for 1 to 2 hours.
 2. A process according to claim 1, wherein the single crystal is that of a semiconducting compound selected from the group consisting of GaP, GaAs, InP, ZnSe and CdS. 